Process for rendering textile materials water repellent



UNITED STATES PATENT OFFICE PROCESS FOR RENDERING TEXTILE MATERIALS WATER REPELLEWT Arnold Doser, Cologne, and Otto Bayer and Karl Hintzmann, Leverkusen I. G.-Werk, Germany, assignors, by mesne assignments, to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 16, 1939, Serial No. 274,025. In Germany May 17, 1938 3 Claims. (Cl. 117-167) The present invention relates to a process for the aid of soap or of non-soapy highly eificient rendering textile materials water-repellent with synthetic emulsifiers like, for instance, condensathe aid oi. zirconium compounds and constitutes tion products of high molecular aliphatic coma further development of the processes described pounds like oleyl alcohol with an excess ethylene in our co-pending application Serial No. 221,452, 5 oxide (see German specification No. 605,973),

filed July 26, 1938. condensation products of colophony and phenols We have found that textile materials of varihaving been'trea'ted with an excess of an alkylene ous origin can be rendered excellently and pe r-, oxide, alkylated phenols, which have been treatmanently water-repellent by impregnating the ed with ethylene oxide (see French patent specimaterials with a water-repellent compound seflcation No. 823,454), condensation products of lected from the group consisting of parafiln, wax higher fatty acids with amino acids (see German and fatty compounds, and with a zirconium compatent specification No. 653,522) and the like. pound, and thereupon treating the material in The said non-soapy synthetic emulsifiers ar esan aqueous neutral to alkaline bath, whereby the pecially suitable when working with zirconium hydrophilic substances are removed therefrom oxychloride, zirconium oxynitrate and the water as far as possible, and finally drying thematesoluble or dispensible hydrolysates obtainable rial at elevated temperature. therefrom. In this case, the water repellent ef- In its most general aspect the present invenfeet is especially good when the quantity of the tion may be carried out with various kinds of emulsifier is as small as possible, for instance, zirconium compounds like, for instance, those 2 equal to about 1 g. per liter of the impregnating compounds which give strongly acid aqueous sobath.

lutions or dispersions like, for instance, zirco- The impregnation of the material with the nium oxychloride, zirconium oxynitrate and the water-repellent organic substances and the zirwater soluble or dispersible hydrolysates obtainconium compounds may be carried out in one or able therefrom, moreover, zirconium sulfate, zirseveral baths. The dry or wet material can be conium acetate, zirconium acetonitrate, zirconium treated, for instance, in a first bath with the formiate, etc. The quantity of the zirconium airconium compound and in'a second vbath with compounds to be used in the present process dea paraffin emulsion. When using the above menpends somewhat on the desired degree of watertioned zirconium compounds which yield strongrepellency, in a manner which is easily underly acid solutions (i. e., zirconium oxychloride, stood by those skilled in the art; the same holds zirconium oxynitrate and the water soluble or true for the n y f P r fi W xes and/0r dispersible hydrolysates obtainabl therefrom), fatty compounds to be used together with the the solutions or dispersions are bufiered to a pH zirconium compounds. Besides zirconium comof about 3.8 to 4.2, for instance, by adding soda, P s. compounds of suitable other metals may sodium acetate, sodium tetraborate, etc. Similar be present, as for instance, soluble or dispersible effects are obtained, if the material, before or compounds of aluminium, chromium, thorium, after impregnation with one of the said par cerium, titanium or of the metal mixtures conticular zirconium compounds, is treated with a tained in monazite sand. A good effect is obneutralizing agent like, for instance, soda, sodium tained already when less than 1% of the ziracetate, sodium tetrabqrate or the like. On the conium compound is brought on the textile maother hand, as above suggested, the paraflin.

terial; if necessary, this quantity may also be wax, or the like emulsion may be added to the increased. In any case, however, the quantities zirconium bath. Particular good results with of zirconium compound necessary for producing such impregnating baths are obtained when usinE the desired result are smaller than those which 5 zirconium oxychloride, zirconium oxynitrate and have been employed in known processes for leadthe water soluble or dispersible hydrolysates oblng silk fabrics. tainable therefrom, and'one of the above menmp lng of the textile material with the tioned highly active synthetic emulsifiers. It is waterrepellent organic substances and with the understood that other finishing compounds may zirconium compounds may be carried out at norbe present in the bath like, for instance, cologmal or elevated temperature, for instance, at phony, synthetic resins and the like- 40-50 C. The water-repellent organic substances After imp e with e S d components are preferably used in the form of aqueous emulthe material is preferably squeezed or centrifuged sions which may be prepared with the aid of and partly or entirely dried. Thereupon it is subsuitable emulsifying agents," for instance, with jected to a treatment with alkalies and/or water which i an important step in the processof the present invention. It is the purpose of this-treatment to remove all hydrophilic substances like, for instance, water soluble electrolytes, soap or other emulsifiers from the material as far as possible. An alkaline treatment will give the desired improved results in all cases, i. e., with every kind of emulsion and zirconium compound. It is carried out by treating the material preferably at elevated temperature with aqueous solutions of the alkalie (caustic soda, sodium carbonate, ammonia, etc.), of alkaline reacting substances like sodium tetraborate, alkali salts of weak organic acids like the sodium salt of acetic acid, methylamino ethane sulfonic acid or methylamino acetic acid, and the like. It is sufilcient when by this alkaline treatment the material is thoroughly wetted. Moreover, it is advantageous that the concentration of alkali is not too high. To the alkaline bath there may further be added small quantities of such wetting agents which can easily be removed by rinsing with water. For instance, solutions are used which contain per liter water 3 gs. soda or 2.5 gs. ammonia and 0.1 g. of the sodium salt of isobutyl naphthalene sulfonic acid. After the alkaline treatment the material is rinsed with water in order to remove the hydrophilic substances as far as possible from the material. It may be mentioned at this point that it is advantageous that from the beginning the quantity of electrolytes and other hydrophilic substances which are brought on the material is not too high so that they can more easily be removed from the material and will not impair the water repellent effect of the process. Finally, the material is again dried, which may be effected, for instance, by simply ironing.

In another modification of our invention, the alkali treatment of the impregnated material may be dispensed with, viz., if the material has been impregnated with a paraffin, wax, etc., emulsion which is free from soap and with a zirconium compound of the group of zirconium oxychloride, zirconium oxynitrate and the water soluble or dispersible hydrolysates obtainable therefrom. In this case it will be suflicient if the impregnated material is ringed with water, preferably at elevated temperatures. The effect is improved if the material has been partially or totally dried between impregnating and rinsing it.

By following the indications given in the present specification it is possible to render all kind of textile material (for instance, cotton, artificial silk and staple fiber from viscose, cuprammonium cellulose and cellulose acetate solutions, wool, silk, mixed material from the afore-mentioned textile fibers, etc.) excellently and permanently water repellent. The results are especially improved in comparison with materials which have not been subjected to the after-treatment with alkalies and/or water, for instance, such as have,; been obtained according to the processes described in our co-pending application Ser. No. 221,452. The water repellent efi'ect is so good that the treated materials in many cases show the so-called pearl-orf-effect, i. e., water which is sprayed on fabrics impregnated according to the present process will immediately pearl off,

leaving hardly and traces on the material. The

water repellent finishes are, moreover, of excellent fastness to wet treatments, for instance, against washing. In most cases, the effect will withstand 5 or more washings with soap or soda without being appreciably impaired. The effect is, moreover, resistant to 'decatising and fulling.

It may be helpful to add a short description of the method according to which the water repellent efiects obtainable according to the present process can be quantitatively measured. The fabric to be tested is sprayed with 1.51 of water of 25 C. from a height of cms. at a pressure of mm. Hg. The difierence in weight of the fabric before and after spraying is measured and calculated in per cent of the original weight. The smaller the increase in weight, the better, apparently, is the water repelling effect.

The process of our invention is more fully illustrated by the following examples without, however, being limited thereto.

Example 1 A light thin fabric of viscose staple fiber is impregnated with an aqueous emulsion containing Gram per 1 liter Parafiin and w 8 So p 4 Zirconium acetate or formiate 25 After drying at 90 C., the fabric is subjected for 10 minutes at 80 C. to an alkaline treatment by means of an aqueous solution of 3 gs./l. sodium carbonate, whereupon it is thoroughly rinsed with water and dried.

The absorption of water amounts to 33% after 1 washing and 4'7 after 5 washings; whereas it is in the untreated tissue.

Example 2 Example 3 A staple fiber fabric according to Example 1, is treated with an emulsion containing paraflin, wax and soap having dissolved therein 24 gs. of zirconium oxychloride (46% ZrOz content) per 1 liter. Thereupon it is squeezed and the fabric is quickly passed through a 0.6% sodium acetate bath. After squeezing the tissue is dried and after-treated as described in Example 1.

The absorption of water amounts to 34% after 1 washing and ZrOz-content) 38% after 5 washings.

Example 4 A dyed woolen fabric is impregnated with an emulsion of paraflin, wax and soap, containing 24 gs. zirconium oxychloride per 1 liter (46% Thereupon the material is centrifuged and dipped for a short time into a bath containing 10 gs./l. of crystallized sodium acetate. After squeezing and drying the impreg nated fabric is dipped for 15 seconds into a bath of 45 C. containing 2.5 gs. ammonia and 0.1 g. of the sodium salt of oleylmethyl taurine per 1 liter. After rinsing with water, drying at elevated temperature and ironing of the still humid fabric, the water absorption amounts to 20% and 16% after 1 washing,

18% after 3 washings and 11% after 5 washings against shown of the untreated fabric.

Example 5 A dyed mixed fabric from wool and viscose staple fiber (1:1) is treated with an emulsion of paraflln, wax and soap, having admixed {therewith 24 g./l. of zirconium oxychloride (46% ZrOz content) and which has been brought to a pH of 4.2 by the addition of sodium carbonate and sodium acetate. After drying at 85 C., the fabric is dipped for 2 minutes into a bath of 40 C., containing 2.5 gs./l. of ammonia and 0.2 g./l. of the sodium salt of burtyl naphthalene sulfonic acid. Thereupon the fabric is well rinsed with water and dried by ironing.

The absorption of water amounts to 8% after 1 washing and 12% after 5 washings.

Example 6 A mixed fabric from wool and viscose staple fiber according to Example 1, is impregnated with an emulsion of parafiin, wax and soap, containing 25 gs./l. zirconium oxynitrate which has been partially neutralized by means of 1.4 gs./l.' sodium carbonate and 6 gs./l. crystallized sodium acetate. After squeezing and drying at 95 C., the fabric is treated for 5 minutes at 90 with a. solution of 3 gs. sodium carbonate in 1 liter water. Thereupon the material is well rinsed with water and ironed.

The absorption of water amounrts to 23% after 1 washing and 31% after 5 washings.

Example 7 When replacing in Example 6 zirconium oxynitrate by 24 gs./l. zirconium sulfate which has been neutralized by means of 10 gs./l. sodium carbonate and 4.8 gs./l. crystallized sodium acetate and working as described in the precedin example, the absorption of water amounts to 27% after one washing and to 38% after 5 washings.

When replacing zirconium oxynitrate by the equimolecular proportion of a zirconium hydroxide sol, which is, for instance, prepared, by dialysis of a zirconium oxychloride solution and which can be employed without any neutralizing operation, the absorption of water amounts to 27% after 1 washing and 27% after 5 washings.

Example 8 A light thin mixed fabric consisting of wool and I Example 9 A mixed fabric from wool and viscose staple fiber is impregnated with an emulsion consistin of paraflin, wax and soap, having incorporated therewith 24 gs. zirconium oxychloride and 12 gs.

borax per 1 liter. After squeezing and drying at 90 0., the fabric is treated for 5 minutes with a solution containing 3 gs. sodium carbonate per 1 liter water. Thereupon it is well rinsed with water and dried. The tissue thus obtained shows an especially soft touch which is not appreciably impaired on repeatedly washing.

The absorption of water amounts to 25% after 1 washing and 27% after 5 washings.

Example 10 Example 11 A loosely woven mixed fabric consisting of'wool and viscose cellulose staple fiber is impregnated with an emulsion containing per 1 liter 3 gs.

parafiin, 2 gs. of a montanic acid ester, 2.5-gs. ammonium oleate and 24 gs. zircon'iumoxychloride (46% ZrOz content) which has been-partially neutralized by means of 18'gs. crystallized sodium acetate. After squeezing and drying in the heat;

the fabric is wetted. with a solution of 90 0. containing 3 gs. of sodium'bicarbonate per 1 liter. Thereupon it is squeezed, well rinsed with water and dried at 90 C. The fabric thus impregnated shows good water repellent properties which are by no means impaired even after several washings.

Example 12 A mixed fabric consisting of wool and viscose staple fiber is impregnated with an emulsion containing per 1 liter water: 7.5 gs. triethanol amineoleate, 3.2 gs. paraflin, 3.2 gs. ceresin, 2.8 gs. montanic acid ester, 24 gs. zirconium oxychloride (46% ZrOa-content) and 0.44 g. aluminum (as hydroxide). Thereupon the fabric is ,squeezed and quickly passed through a 0.6% sodium acetate bath. After drying at 90 C., the fabric is treated for 2 minutes at -90 C. with a solution of 3 as. soda+0.3 g. of the sodium salt of oleyl methyl taurine per 1 liter water, whereupon it is for several times rinsed with water and dried at elevated temperature. The absorption of water amounts to 31% after 1 washing and after 5 washings.

Example 13 A wet mixed fabric consisting of cotton and viscose staple fiber is treated on the jigger with an emulsion containing per 1 liter water 20 gs. of a weakly acid aqueous emulsion of paraflin (20%), glue (8%), aluminium hydroxide gel (6%), colophony (1%), 24 gs. zirconium oxychloride (46% ZrOz content) and 4 gs. sodium acetate. Thereupon the fabric is passed through a 0.7% sodium acetate bath. After drying at about C., the fabric is treated with a hot 0.3% sodium carbonate solution and then with a 0.1% warm soap solution and subsequently well rinsed with water. The fabric thus impregnated shows excellent water repellent properties.

Example 14 A fabric of viscose artificial silk having been pre-treated by means of a 0.2% soap solution and rinsed, is impregnated in the Wet state with an emulsion as described in Example 13 having dissolved therein. in addition. gs. borax. After having been squeezed and dried at 85 C., the fabric is treated for a short time with a 0.3% sodium carbonate solution at 90-95, whereupon it is several times rinsed with water and dried by ironing.

The absorption of water amounts to 32% after 1 washing and 33% after 5 washings.

Example The following impregnation bath is prepared: 62.5 gs. of an emulsion consisting of 8% parafiln, 8% ceresin, 7% artificial wax (montanic acid ester), 2% of an emulsifier (obtained by the condensation of oleyl alcohol with several mols ethylene oxide) and 75% water are pasted with 600 ccms. water of 70 C. This emulsion is added to a solution of 12 gs. zirconium oxychloride (46% ZrOz-content) in 300 ccms. water of 70 C. At 65 C. there are stirred into this bath 30 ccms. of a 10% aqueous sodium carbonate solution and, after cooling to 45 C., 2 ccms. glacial acetic acid and 1.2 gs. crystallized sodium acetate aqueous solution). The bath shows then a pH of 3.9.

In this bath one of the following textile materials is treated at 45 C. for 1 minute: a loosely woven viscose staple fiber fabric, smooth undyed viscose artificial silk fabric, cellulose acetate artificial silk fabric, freshly precipitated deacidified loose cuprammonium cellulose staple fiber, dyed densely woven cotton popeline fabric (fabric for mackintoshes), thin loosely woven wool fabric, mixed fabric consisting of wool and viscose staple fiber (1:1) and a schappe silk fabric. Thereupon the materials are squeezed and dried in the usual manner. Before the first washing the materials are drawn for 1 minute through water of 95 C., whereby they are immediately wetted; they are then rinsed for a short time with water and dried in the drying-oven at 85- 95 for 30 minutes. The materials thus impregnated show an excellent pearl-off-eifect which is not impaired even after the fifth washing; they are, furthermore, fast to decatizing. The cuprammonium cellulose staple fiber is capable of being fulled for 32 hours without showing any decrease in its water-repellent capacity.

The treatment with hot water can also be carried out at lower tempertures, temperatures over 80 0., however, being preferred, since a more quickly wetting of the fabrics is effected thereby.

Example 16 'of oleyl alcohol with several mols ethylene oxide) and water are pasted with 250 ccms. water of C. On the other hand, 12 gs. zirconium oxychloride (46% ZrO2 content) are dissolved at 50C. in 200 ccms water, whereto ccms. 10% sodium carbonate solution and 2 ccms. glacial acetic acid are added. After cooling to 25, the wax solution is stirred into the zirconium salt solution, whereupon A; liter water and 7.5 ccms.

of a 20% aqueous solution of crystallized sodium acetate are added. The emulsion shows then a pH of about 3.9.

With this impregnating bath the fabrics mentioned in Example 15 are treated, the viscose staple fiber, artificial silk and cotton for 1 minute, the fabrics containing wool and silk only for 10 seconds. The fabric are then squeezed and dried, with the exception of the silk, by exposing to the air for hour. Thereupon the fabrics are dipped for 1 minute into hot water of 97, shortly rinsed and dried in the drying oven at -95 for 30 minutes. In all cases, an excellent and permanent pearl-off-eifect is reached, the fabrics showing, furthermore, a good fastness to decatizing. In the case of the viscose artificial silk it is advantageous to completely dry the fabric before subjecting it to the treatment with Example 17 An aqueous paraffin emulsion is prepared containing 10% paraflin, 10% ceresin, 8.75% artificial wax (montanic acid ester), 5% oleic acid, 0.7% sodium hydroxide and 1.25%v of a condensation product of oleyl alcohol with several mols. ethylene oxide. 50 gs. of this emulsion are stirred into 350 ccms. water at 50 C. This solution is stirred at 45 C. into a solution of 12 gs. zirconium oxychloride (46% Zr02-content) in 200 ccms. water, whereupon there are added 30 ccms. of a 10% aqueous sodium carbonate solution, 2 ccms. glacial acetic acid, 350 ccms. water of 25 C. and 1.2 gs. crystallized sodium acetate in form of a 20% aqueous solution. The impregnating bath thus prepared shows a pH of 3.9. The content of oleic acid imparts to the original paraffin emulsion a good stability and reduces the tendency of foaming of the bath.

In the bath thus prepared the textile fabrics mentioned in Example 15, are dipped for 1 minute at 40 C., whereupon they are squeezed, so that the viscose staple fiber fabric shows an increase in weight of 115% and then allowed to lay for hour. The fabrics are then dipped into water of C. for 1 minute, shortly rinsed with water and dried for 30 minutes in the drying oven at 85-95 C. All fabrics thus impregnated show an excellent and permanent water-repellent effect. The water-treatment can be carried out at 70 C. with a similar result.

Example 18 A dyed acetate artificial silk satin is impregnated with an emulsion containing per liter water 8 gs. paraflin and wax, 4 gs. soap and 24 gs. zirconium oxychloride and which is partly neutralized by addition of sodium acetate to a pH of 4.2.

The fabric is thereupon for a short time (15 sec.) immersed into an aqueous bath of 40 C. containing per liter 0.25 g. ammonia and 0.1 g. of the sodium salt of oleyl methyl taurin.

Thereafter the fabric is thoroughly rinsed with water and dried.

By this treatment the fabric has acquired Water repellent properties of outstanding quality:

The absorption of water of the fabric before washing the same is 3%, and after five washings 5%. i. e., the fabric does not practically take up any water.

The "pearl-off effect is excellent.

We claim:

1. Process for rendering textile material water at a pH of 3.8-4.2 and containing paraffin, wax, a

smallquantity of a fatty acid, zirconium oxychloride and a condensation product of oleyl alcohol and of several molecular quantities of ethylene oxide serving as emulsifying agent, thereupon rinsing the material with hot water, whereby the hydrophilic substances are removed therefrom as far as possible, and finally drying the material at elevated temperature.

3. A process as in claim 1 i/n which the textile material is cellulose acetate.

ARnoLD DOSER. o'r'i'o BAYER. KARL HINIZMANN. 

